ACS Organic & Inorganic Au最新文献

{"title":"Silver-Catalyzed C(sp³)-H Functionalization.","authors":"Masoud Sadeghi","doi":"10.1021/acsorginorgau.5c00104","DOIUrl":"10.1021/acsorginorgau.5c00104","url":null,"abstract":"<p><p>Silver catalysis has emerged as a versatile tool for C-(sp³)-H bond functionalization, offering unique opportunities to transform simple hydrocarbons into valuable products. Both activated and unactivated C-(sp³)-H bonds have been investigated in recent years. However, most studies have focused on activated bonds. In these protocols, in situ generation of nitrene intermediates has dominated the field, enabling efficient and selective C-(sp³)-H bond transformations. These reports demonstrate that ligand design, in addition to the nature of the silver catalyst, plays a crucial role in achieving chemo-, site-, and even stereoselectivity. During the past decade, silver-catalyzed functionalization has been used for the conversion of C-(sp³)-H bonds into C-C, C-N, C-O, and C-X (X = halogen) bonds. These protocols have shown that Ag-(I) combined with suitable oxidants can be used as a powerful synthetic tool for the functionalization of specific C-(sp³)-H bonds into desired C-Z bonds. This review highlights the advances and limitations in silver-catalyzed C-(sp³)-H functionalization that have been reported during the past decade.</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"6 1","pages":"23-40"},"PeriodicalIF":3.3,"publicationDate":"2025-10-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12879210/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146143550","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Modeling 2D van der Waals Materials with Homonuclear Bonds of Main Group Cations.","authors":"Peng Yan, Anthony A Casale, Joseph W Bennett","doi":"10.1021/acsorginorgau.5c00096","DOIUrl":"10.1021/acsorginorgau.5c00096","url":null,"abstract":"<p><p>We survey a range of 2D van der Waals (vdW) layered materials that contain homonuclear bonds of main group elements, specifically Ga-Ga, In-In, Si-Si, Ge-Ge, and P-P, using first-principles density functional theory (DFT) methods. The covalent bonding and geometries present in these materials can stabilize oxidation states that differ from those found in conventional semiconductors composed of main group elements, such as Si, InP, and GaAs. Since 2D vdW materials did not gain widespread use until recently, many have been excluded from the first-principles test sets developed over a decade prior, where the focus was on determining the accuracy of potentials used in different modeling methods. In this study, we benchmark the set by exploring a range of modeling methods that include GGA and meta-GGA exchange-correlation functionals commonly used in first-principles DFT methods, as well as exact exchange introduced using HSE06 and PBE0. We investigate their effects on the ground-state structure, electronic band structure, and computational cost and report on this benchmarking data. Our test set of 2D vdW materials contains multiple structural types that span binary, ternary, and quaternary compositions, including ferroic ground states. We found that the vdW-corrected GGA is capable of accurately capturing lattice constants (within ±2% relative to available experimental data) across various 2D vdW materials in our test set, with relatively low computational cost and turn-key compatibility with the open-source code Quantum Espresso. Additionally, vdW-corrected GGA can reliably identify stable ferroelectric and ferromagnetic ground states, can be used to determine trends in electronic band structure, and serve as a starting point for predicting more accurate band gaps. The predicted electronic band structure and corresponding projected density of states (PDOS) are crucial for establishing the connection between microscopic properties and atomic or molecular orbitals, which can, in turn, be used to predict novel functional 2D vdW materials.</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"6 1","pages":"104-118"},"PeriodicalIF":3.3,"publicationDate":"2025-10-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12879168/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146143507","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Role of Propionate Side Chain in Heme-Containing Metalloenzymes.","authors":"Dinesh Singh, Vandana Kardam, Kshatresh Dutta Dubey","doi":"10.1021/acsorginorgau.5c00078","DOIUrl":"10.1021/acsorginorgau.5c00078","url":null,"abstract":"<p><p>Propionate side chains are essential structural components of porphyrin-based metalloenzymes. While numerous studies have investigated the functional significance of propionate side chains from various perspectives, comprehensive reviews focusing specifically on their roles in catalytic mechanisms remain scarce. Traditionally, the role of propionate has been limited to substrate binding and heme stabilization; however, emerging evidence from studies published particularly after 2005 highlights its involvement in a range of noncanonical functions, including water gating, oxidant formation, and electron transfer. This review aims to bridge the gap in existing literature by systematically discussing these expanded roles and emphasizing the broader mechanistic importance of propionate side chains in metalloenzymes, particularly the iron-containing enzymes.</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"5 6","pages":"451-466"},"PeriodicalIF":3.3,"publicationDate":"2025-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12679310/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145701858","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Recent Advances in C-H Perfluoroalkyl Thiolation and Perfluoroalkyl Sulfonylation.","authors":"Sichang Wang, Liying Zhang, Fei Hong, Weichao Du, Congyu Ke, Jie-Ping Wan","doi":"10.1021/acsorginorgau.5c00094","DOIUrl":"10.1021/acsorginorgau.5c00094","url":null,"abstract":"<p><p>This review comprehensively summarizes the recent advances in the direct C-H perfluoroalkyl thiolation and perfluoroalkyl sulfonylation, focusing on the incorporation of -SCF₃ and -SO₂CF₃ motifs. Due to their exceptional lipophilicity, electron-withdrawing nature, and metabolic stability, these fluorine-containing groups are highly valuable in pharmaceutical, agrochemical, and material sciences. The contents of this review are systematically organized according to the hybridization of the central carbon atom (sp, sp², sp³) and cover both transition-metal-catalyzed and transition metal-free methodologies. Key developments in electrophilic trifluoromethylthiolating reagents, such as hypervalent iodine compounds, <i>N</i>-trifluoromethylthiosaccharin, and related derivatives, are highlighted. The mechanism, scope, limitation, and application of typical reactions are discussed, emphasizing strategies to overcome challenges in regioselectivity and functional group compatibility. The review also explores emerging trends in photocatalytic, electrochemical, and dual catalytic systems, underscoring the move toward more sustainable and efficient synthetic routes. Finally, future perspectives and potential applications in the synthesis of bioactive molecules and functional materials are discussed.</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"5 6","pages":"467-484"},"PeriodicalIF":3.3,"publicationDate":"2025-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12679318/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145701826","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Synthesis and Electronic Structure of a Tetraazanaphthalene Radical-Bridged Yttrium Complex.","authors":"Saroshan Deshapriya, Selvan Demir","doi":"10.1021/acsorginorgau.5c00086","DOIUrl":"10.1021/acsorginorgau.5c00086","url":null,"abstract":"<p><p>Taming radical anions with highly electropositive metal ions poses a grand synthetic challenge owing to the high reactivity of such compounds originating from the unpaired electron. A successful synthetic metal radical match elicits a desire to thoroughly understand the electronic structure of a given metal radical pairing, which may inform about the potential physical properties pertaining to spintronics and magnetism relevant for future technologies. Here, the 1,4,5,8-tetraazanaphthalene (tan) ligand was utilized in the synthesis of (Cp*₂Y)₂(μ-tan), <b>1</b>, using the doubly reduced version K₂tan and Cp*₂Y-(BPh₄) following a salt metathesis reaction. Chemical oxidation of <b>1</b> yielded [(Cp*₂Y)₂(μ-tan^•)]-[BArF₂₀], <b>2</b>, containing a tan^-• radical anion. <b>2</b> constitutes the first <i>d</i>-block coordination compound bearing a tan radical. <b>1</b> and <b>2</b> were studied through X-ray crystallography, electrochemistry, and spectroscopy. The radical nature of <b>2</b> was uncovered by cw-EPR spectroscopy and density functional theory (DFT) computations. All findings suggest major changes in the spin and charge distributions of this organic radical ligand when it is metalated. In fact, the results demonstrate that the tan^-• radical is more stable when coordinated to a transition metal than in its free nature, and thus, this insight is relevant for the development of future spintronic technologies.</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"5 6","pages":"557-566"},"PeriodicalIF":3.3,"publicationDate":"2025-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12679307/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145702146","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Co₃O₄‑Promoted Cerium Oxide Catalyst for Efficient Catalytic <i>N</i>‑Alkylation of Amines with Alcohols.","authors":"Jianyao Kou, Guangyao Yang, Zhixin Yu, Jiachao Liu, Yuhang Xu, Zhuo Xin, Yuxing Huang","doi":"10.1021/acsorginorgau.5c00069","DOIUrl":"10.1021/acsorginorgau.5c00069","url":null,"abstract":"<p><p>The use of heterogeneous catalysts to generate amine compounds through anaerobic <i>N</i>-alkylation of alcohols via hydrogen transfer strategy is a highly promising synthetic strategy, as it can construct C-N bonds under relatively mild and green conditions. Moreover, amine compounds are widely used in the synthesis of pharmaceutical intermediates, agriculture and fine chemicals. In this work, we successfully constructed a novel Co₃O₄/CeO₂ catalyst using the hydrothermal synthesis method and applied it to the <i>N</i>-alkylation reaction of alcohols, achieving up to 99% of the target product yield with broad substrate scope and high catalyst stability. The Ce³⁺/Ce⁴⁺ redox pairs and oxygen vacancies in the CeO₂ support with highly dispersed Co species synergistically catalyze the hydrogen borrowing process of alcohols and amines to generate secondary amines with high activity and selectivity.</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"5 6","pages":"498-506"},"PeriodicalIF":3.3,"publicationDate":"2025-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12679301/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145701713","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Guest-Induced Conformational Switching in \"One Wall\" Calix[4]pyrrole Cavitands Functionalized with an Inwardly Directed Carboxylic Acid.","authors":"Mingkai Zhao, Andrés F Sierra, Gemma Aragay, Pablo Ballester","doi":"10.1021/acsorginorgau.5c00087","DOIUrl":"10.1021/acsorginorgau.5c00087","url":null,"abstract":"<p><p>We report the design, synthesis, and conformational analysis of two aryl-extended calix[4]-pyrrole (AE-C[4]-P) cavitands that feature a single methylene bridge and an opposed aromatic bridging wall with an inward-facing carboxylic acid. Inspired by Rebek's introverted acid motif, these cavitands were developed to explore guest-induced conformational switching between \"equatorial\" and \"axial\" orientations of the bridging aromatic wall. Binding studies with <i>N</i>-oxide guests, capable of monotopic or ditopic hydrogen bonding, revealed that the nature of the bridging aromatic spacer critically governs the host behavior. The benzimidazole-based cavitand showed strong affinity for DABCO mono-<i>N</i>-oxide but resisted conformational change. In contrast, the quinoxaline-imidazole analogue underwent a solvent-dependent switch from \"equatorial\" to \"axial\" geometry upon binding 4-carboxy-pyridine-<i>N</i>-oxide guest. This switching is driven by the ditopic binding of the guest and stabilized by two intramolecular CH···lone pair interactions in the axial conformer of the complex. DFT calculations supported the experimental results. The reported findings highlight key structure-function relationships in calix[4]-pyrrole cavitands and establish a general strategy for designing guest-responsive molecular containers capable of conformational switching.</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"5 6","pages":"567-581"},"PeriodicalIF":3.3,"publicationDate":"2025-10-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12679308/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145701843","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Copper(I)-Anchoring Covalent Organic Polymer for Heterogeneous CuAAC Reaction without Reducing Agents and Copper Leaching.","authors":"Maria Aurora Guarducci, Simone Manetto, Andrea Giacomo Marrani, Francesco Amato, Paolo Guglielmi, Michele Coluccia, Antonella Fontana, Serena Pilato, Claudio Villani, Alessia Ciogli, Giulia Mazzoccanti","doi":"10.1021/acsorginorgau.5c00067","DOIUrl":"10.1021/acsorginorgau.5c00067","url":null,"abstract":"<p><p>A novel copper-(I)-anchored covalent organic polymer (Cu⁺@COP) is presented as a robust, heterogeneous catalyst for copper-catalyzed azide-alkyne cycloaddition (CuAAC), operating without the need for external reducing agents or observable copper leaching. Cu⁺ stabilization is achieved via multidentate N,O-ligand coordination within the polymer matrix, enabling high catalytic efficiency (up to 95% yield) and recyclability. Structural, spectroscopic, and ICP-OES analyses confirm Cu presence, offering an alternative to traditional CuAAC protocols. This system combines operational simplicity, reduced waste, and green chemistry principles, positioning Cu⁺@COP as a practical catalyst for applications in synthetic and materials chemistry.</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"5 6","pages":"507-517"},"PeriodicalIF":3.3,"publicationDate":"2025-09-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12679302/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145701624","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Electrochemical Halogenation and Etherification of Alcohols Enabled by a Halide-Coupled Phosphine Oxidation.","authors":"Emma A Hale, Vincent Tc Ngo, Qilei Zhu","doi":"10.1021/acsorginorgau.5c00091","DOIUrl":"10.1021/acsorginorgau.5c00091","url":null,"abstract":"<p><p>Phosphine-mediated nucleophilic substitution reactions of alcohol substrates, such as the Appel and Mitsunobu reactions, have found widespread applications in chemical synthesis. However, their reliance on stoichiometric chemical oxidants (e.g., carbon tetrachloride and azodicarboxylate reagents) often results in limited functional group tolerance, environmentally hazardous wastes, and unsatisfactory reaction economy. Herein, we describe a user-friendly electrochemical Appel reaction employing readily available tetrabutylammonium halide salts ( ^<i>n</i> Bu₄N⁺X^-, X = Cl, Br, and I) as the halogen source. A survey of alcohol substrates revealed broad functional group tolerance, including complex pharmaceutical and bioactive scaffolds. Electroanalytical voltammetry and control experiments support a halide-coupled phosphine oxidation pathway under mild anodic potentials, affording key alkoxyphosphonium intermediates prior to nucleophilic substitution. Notably, the electrochemical halogenation conditions can also facilitate intramolecular alcohol etherification with oxidation-sensitive phenols and weakly acidic alcohol nucleophiles.</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"5 6","pages":"492-497"},"PeriodicalIF":3.3,"publicationDate":"2025-09-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12679309/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145701857","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Stereoselective <i>E</i>‑Carbofunctionalization of Alkynes to Vinyl-Triflates <i>via</i> Gold Redox Catalysis.","authors":"Filippo Campagnolo, Lorenza Armando, Elisa Boccalon, Alessandra Cicolella, Manfred Bochmann, Giovanni Talarico, Luca Rocchigiani","doi":"10.1021/acsorginorgau.5c00084","DOIUrl":"10.1021/acsorginorgau.5c00084","url":null,"abstract":"<p><p>Carbofunctionalization of alkynes with trifluoromethylsulfonate nucleophiles is a powerful strategy for the synthesis of vinyl triflates with diverse molecular complexity. However, stereoselective protocols are challenging to realize, and the development of novel strategies for controlling the selectivity is highly desirable. In this work, we show that gold complexes bearing the hemilabile MeDalPhos ligand (MeDalPhos = di-(1-adamantyl)-2-dimethylamino-phenylphosphine) catalyze the <i>E</i>-stereoselective carbofunctionalization of internal alkynes using aryl/vinyl iodides and AgOTf as simple starting reagents. Based on the outer-sphere nature of this reaction and the beneficial effect of the MeDalPhos ligand, the <i>Z</i>-selective attack is practically suppressed, leading to an ideal kinetic selectivity. Mechanistic studies, both experimental and theoretical, revealed that the interplay between kinetics and thermodynamics is crucial in determining the final <i>E</i>/<i>Z</i> ratios for each substrate.</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"5 6","pages":"548-556"},"PeriodicalIF":3.3,"publicationDate":"2025-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12679304/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145701969","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}